Monoazo dyestuffs containing a 4-organoamino - methylene - 1 - hydroxynaphthalene-2-carboxylic acid group



United States Patent 3,492,285 MONOAZO DYESTUFFS CONTAINING A 4-OR-GANOAMINO METHYLENE 1 HYDROXY- NAPHTHALENE-2-CARBOXYLIC ACID GROUP HeinzMachatzke, Leverkusen, Germany, assignor to Farbenfabriken BayerAktiengesellschaft, Leverkusen, Germany, a corporation of Germany NoDrawing. Filed July 11, 1966, Ser. No. 563,957 Claims priority,application Germany, July 15, 1965, F 46,602; Apr. 6, 1966, F 48,880Int. Cl. C07c 107/08 U.S. Cl. 260-151 10 Claims ABSTRACT OF THEDISCLOSURE Azo dyestuffs, which dyestuffs are used for dyeing andprinting wool, silk or superpolyamide fibers with good fastness towashing, and the 2:1 metal, e.g. Cr, Co, Ni, complexes thereof, of theformula (EHg-NOORZ The present invention relates to new azo dyestuffs ofthe formula X Y I CHz-NO CR2 and metal complex compounds thereof. InFormula I, A means a radical of the benzene or naphthalene series inwhich Y is in the o-position to the azo group, Y is a metalcomplex-forming grouping, X an OH group, R stands for hydrogen or alower alkyl radical, and R is an alkyl, alkenyl, aryl, alkoxy, amino,monoalkylamino, dialkylamino or phenylamino radical which may besubstituted.

As metal complex compounds of the dyestufis (I) the chromium, cobalt,copper and nickel complexes are of special interest.

Examples for metal complex-forming groups Y are OH, COOH, OCH and OC HThe new azo dyestuffs are obtained in that the diazo compound of anamine of the formula 1 A-NHz (II) in which the groups -Y and NH in theradical A 3,492,285 Patented Jan. 27, 1970 "ice stand in the o-positionto each other, is coupled with a compound of the general Formula III orIV OR U 5 (III) r same meaning as above. If using the components (III)the coupling reaction takes place with the exchange of the COOH group inthe fi-position of the coupling component (III) for the azo group.

To roduce 1:2 chromium or 1:2 cobalt complex dyestuffs, i.e thosedyestuffs which contain for each atom of chromium or cobalt about twomolecules of the dyestuff in complex linkage, two identical or twodifferent dyestuffs of the Formula I can be employed, or a dyestulf (I)and any other metallisable azo dyestuff. Chroming or cobalting ispreferably effected by known methods in a weakly acid, neutral oralkaline medium with the use of approximately 0.5 mol of the heavy metalcompound for each mol of the metallisable azo dyestuff.

To produce uniform 1:2 mixed chromium complex dyestuffs the process maybe carried out in such a way that first one mol of a metallisable azodyestuff (I) and one gram atom of a chromium-III-salt are heated in anacid medium until the 1:1 chromium complex is formed, which is thenreacted with one mol of another metallisable azo dyestuff of the FormulaI or with another metallisable azo dyestuff, e.g. a dyestulf which isdifierent from (I), of the general formula wherein D means a radical ofthe benzene or naphthalene series in which Y is in the o-position to theazo group, B represents the radical of a coupling component whichcontains Z linked in the o-position to the azo group, Y stands for ametal complex-forming grouping, and Z for an OH, NH or NI-I-alkyl group.

Diazo components suitable for the synthesis of the new dyestuffs, arethe following compounds inter alia: Z-aminophenols, such as3amino4-hydroxybenzene-Z-methylenesulphone-l-ether,

Z-aminobenzoic acid, 2-amino-4-sulphonamido-benzoic acid,

Z-amino-S-sulphonamindobenzoic acid,

Z-methoxy-l-aminobenzene,

2,4-dirnethoxy-l-aminobenzene,

2-methoxy-4-chloro-l-aminobenzene, or

6-nitro-2-hydroxyl -aminonaphthalene-4-sulphonic acid.

The following compounds are suitable coupling components (III) and (IV),for example:

4-chloroacetylamin-omethylene-l-hydroxynaphthalene- 2-carboxylic acid,4-chloropropionylarninomethylenel -hydroxynaphth alene- Z-carboxylicacid,4-(N-methyl-N-chloroacetylamino)-methylene-l-hydroxynaphthalene-Z-carboxylicacid, 4-acetylaminomethylene-l-hydroxynaphthalene-2- carboxylic acid,4-propionylaminomethylenel -hydroxynaphthalene-2- carboxylic acid,4-(N-methyl-N-acetylamino)-methylene-l-hydroxynaphthalene-Z-carboxylicacid, 4-(N-methyl-N-benzoylamino)-methylene- 1-hydroxynaphthalene-Z-carboxylic acid,4-dichloroacetylaminomethylene-l-hydroxynaphthalene- 2-carboxylic acid,4-trichloroacetylaminomethylene-l-hydroxynaphthalene- 2-carboxylic acid,4-acryloy1amino-methylene-l-hydroxynaphthalene-2- carboxylic acid,4-chloroacryloylaminomethylene-l-hydroxynaphthalene- 2-carboxylic acid,4-trichloroacryloylaminomethylene-l-hydroxynaphthalene-Z-carboxylicacid, 4-methcaryloylaminomethylene-l-hydroxynaphthalene- 2-carboxylicacid, 4-butyrylaminomethylenel-hydroxynaphthalene-Itcarboxylic acid,4-crotylaminomethylene-l-hydroxynaphthalene-Z- carboxylic acid,4-'y-chlorocrotylaminomethylene-1-hydroxynaphtha1ene- 2-carboxylic acid,4-vinylacetylaminomethylene-l-hydroxynaphthalene-2- carboxylic acid,4-methylsulphonyl-hydroxyacetylaminomethylene-lhydroxynaphthalene-Z-carboxylicacid,4-methylsulphonyl-fi-hydroxypropionylamino-methylenel-hydroxynaphthalene-Z-carboxylicacid,443-methylsulphonylpropionylaminomethylene-l-hydroxynaphthalene-Z-carboxylicacid,4-fl-phenylsulphonylpropionylaminomethylene-l-hydroxynaphthalene-2-carboxylicacid, 4-benzoylaminomethylene-l-hydroxynaphthalene-Z- carboxylic acid,4-p-bromomethyl-benzoylaminomethylene-l-hydroxynaphthalene-Z-carboxylicacid,4-p-chlorornethyl-benzoylaminomethylene-l-hydroxynaphthalene-Z-carboxylicacid or the aforementioned compounds being free of the 2- positionedcarboxylic acid group according to Formula IV.

The coupling components (III) are obtained, for example, by reactingmethylolamides or their methyl or ethyl ethers withl-hydroxynaphthalene-Z-carboxylic acid in the presence of stronglyacidic condensing agents, e.g. 80- 100% sulphuric acid, mixtures ofglacial acetic acid and hydrochloric acid or alcoholic hydrogenchloride.

The coupling components (IV) are obtainable, for example, by heatingcomponents of the Formula III in minerai acid medium with the additionof hydrogensulphate whereupon the Z-standing carboxylic acid group issplit off.

The new dyestuffs, in the form of their metal complex compounds, areeminently Suitable for the dyeing and printing of natural or regeneratedprotein fibres, such as wool, silk, as well as for the dyeing andprinting of synthetic fibres, such as superpolyamide fibres. When usedas metal-free dyestuffs they can be after-treated on the fibre or in thedye-bath with metal-yielding agents.

In the following examples, which are given for the purpose ofillustrating the invention, the parts are parts by weight; thetemperatures are given in degree centigrade.

EXAMPLE 1 45 parts 4 chloroacetylaminomethylene-l-hydroxynaphthalene-Z-carboxylic acid are dissolved in 500parts Water by the addition of a 20% sodium hydroxide solution. Theproduct is cooled to 0 by the addition of 400 parts ice and the'diazonium salt suspension, prepared by the diazotisation of 23 parts4-nitro-2-aminophenol in 300 parts water, is allowed to run in. Duringcoupling, a pH value of 13-14 is maintained by the addition of aconcentrated sodium hydroxide solution. After one hour the precipitateddyestufr is filtered off with suction and washed with water.

The dyestuti paste obtained is added at 90 to a solution of 21 partscobalt-II-sulphate, and 16 parts sodium acetate in 350 parts water and120 parts formamide. The reaction mixture is stirred at 80 for 2 hours,then allowed to cool and filtered oil with suction. The dyestuff pasteis suspended in 1000 parts water, heated at 80-90 for 30 minutes andfiltered off with suction. The dyestufi paste is subsequently dried at60-70 in a vacuum. 60 parts of the metal complex dyestutf of thestructure are obtained, which dyes polyamide fibres in garnet shades.

EXAMPLE 2 45 parts4-chloroacetylamino-methylene-l-hydroxynaphthalene-Z-carboxylic acid aredissolved in 500 parts water by the addition of a 20% sodium hydroxidesolution. The solution is cooled to 0 by the addition of 400 parts iceand a diazonium salt solution, which was prepared by the diazotisationof 19.3 parts 4chloro-2- aminophenol in 300 parts water, is allowed torun in. A pH value of l3l4 is maintained during the coupling by theaddition of a concentrated sodium hydroxide solution. The precipitateddyestuff is filtered off with suction after one hour and then washedwith water. The dyestufi? paste is dissolved at in 30 parts formamideand 11 parts potassium dichromate are added. After five hours, themixture is poured into 2000 parts water containing 200 parts sodiumchloride previously dissolved, the precipi tated dyestufi is filteredoff with suction and dried at 60- 70". 48 parts of the metal complexdyestufiE of the formula 6 EXAMPLE 3 10 parts of the dyestuff which canbe obtained accord- CHNHCOGHCPG ing to Example 1 are ground with 10parts of a naphthalene/ formaldehyde condensation product and stirredinto 5 10,000 parts Water at pH 6. parts of a levelling agent, e.g. analkylphenyl-polyglycol ether, are added. 1000 parts of a fabric ofsynthetic polyamide fibres are 4 introduced into this dyebath and thetemperature is slowly 9 1O raised to 100. After dyeing at thistemperature for 1 Na hour, the fibre material is rinsed, Washed anddried. A O garnet coloured dyeing with very good fastness to light NZNand Wet processing is obtained.

l EXAMPLE 14 CHuNHCOOHaCI 10 parts of the dyestuff which can be obtainedaccordf d h d e nav blu ing to Example 1 are ground with 10 parts of anaphthaare 0 mm W 1c y 8 p0 yaml e r m y a lene/formaldehydecondensation product and stirred into shades of excellent fastnessproperties.

When the procedure is followed as described in Exloooo parts water at PH10 parts of a levelhng agent amples 1 and 2 and, instead of the diazoand coupling an alkylphenyl'ployglyc ol ether are added 1000 componentsthere mentioned, the components set out in Parts of a hank of aremqoduced Into thls dyebath Table I are used, f ll d by cobalting orchroming the and the temperature is slowly ralsed to 100. After dyeingdyestuffs obtained, further dyestuffs with very good thls temperature 1hour, the fibre l r al 1S fastness to light and wet processing areobtained which rlnsed, Washed and drled- A garnet coloured y g Wllih dyepolyamide and protein fibres in the indicated shades. very good fastnessto light and wet processing is obtained.

TABLE I Coupling component;

HOOG

CHgIII-C O-Rg Diazo component Metal R R2= Shade 4-nitro-2-aminophenol CoH CH3 Garnet.

D 00 H CsHs D0.

D0. Cr H CHzCl Currant.

Do Cr H CHzCHzCl o. 4-chloro-2-aminophenol Co H CHzCl Bordeaux.

Do Co H CH3 Do.

0 00 H CHzCHzCl Do. 4,6-dinitro-2-aminophenol. Cr H CHzCl Grey.

Cr H CsHa Do. 2-aminophenol-4-sulphonamide Cr H OHgCl Currant.

Do 00 H CHzCl Bordeaux. 2amlnophenol-4-ethylsulphon Co H CHgC]. Do.6'ehloro-4-nitro-2-aminophenol Cr H CHzCl Currant.

H CHnCl Red-violet-brown. H CHzCl Bordeaux. H CHiCl Currant. H CHiClBordeaux. H CH3 Blue-violet. H C2H5 Do. H CeHa D0. CH3 CaHs D0.

H (3=CH2 Do.

H OH=OHQ Do. H -CHgCHqCl Do. H NH; Bordeaux. H NHCHa o. H NHC4H9Blue-violet. H N(CH3)z D0. H OC2H5 DO. H OCH3 D0. H --CH1CI Grey-violet.H CH Cl Red-violet. H NHO6H5 D0. H CHzCl Navy-blue. H OHzCl Blue. HCHzCl Bordeaux. 0 H CH Cl Currant. 2-aminophenol-4-(2-hydroxyethyl) HCHzCl Bordeaux.

sulphonamide. 4-chloro-5-m'tro-2-amlnophenol C0 H CHiCl Blue.

H CHgCl Blue-violet. H CHaCl Currant. o Cr H CH Cl Grey-blue.6-nitro2-hydroxy-l-aminonaphthalene-- Cr H CHaCl Black-grey.

sulphonic acid. 4,6-dmitro-2-aminophenol 00 H CHgOl Brown.

7 EXAMPLE 5 141 parts of a 20% paste of 4-chloroacety1aminomethylene 1hydroxynaphthalene 2 carboxylic acid are slurried in 1000 parts of waterand 50 parts of a 15% solution of sodium hydrogen sulphite added.Hydrochloric acid is added subsequently until a pH of 2 to 6 is reachedand the mixture then heated with stirring to the boil for 4 to 5 hours.After this time 4-chloroacetylaminomethylene 1 hydroxynaphthalene hasprecipitated as a half solid mass at the bottom of the vessel. Themixture is cooled down to to 10 C., the precipitated product dissolvedwith 10 parts of concentrated soda-lye, 40 parts of sodium carbonateadded and a diazo suspension prepared from 15.4 parts of-nitro-2-aminophenol added dropwise within minutes; the mixture isstirred for 5 hours at 0 to 10 C. It is then acidified with dilutehydrochloric acid and the precipitated dyestuif filtered with suction.The dyestutf paste is suspended in 1000 parts of water at pH 8 to 9,warmed to 50 to 70 C. and a solution of 22 parts of cobalt sulphate and5 parts of tartaric acid in 100 parts of water added dropwise withinminutes while keeping the pH at 8 to 9 by adding dropwise sodiumhydroxide. After further stirring for 4 hours at 50 to 70 C. theprecipitated cobalt containing dyestuff is filtered hot With suction.After drying one obtains 43 parts of the cobalt complex dyestuff of theformula which dyes synthetic superpolyamide fibres and wool navy blueshades.

EXAMPLE 6 28 parts of 4 chloroacetylaminomethylene 1 hydroxynaphthaleneare dissolved in 500 parts of water together with 10 parts of 20%soda-lye at 0 to 5 C. 40 parts of sodium carbonate are added andsubsequently a diazo suspension obtained by diazotisation of 10.9 partsof 2 aminophenol with nitric acid is added within 10 minutes. Thereaction mixture is stirred at pH 7 to 9 for 4 hours, acidified withdilute hydrochloric acid and the dyestuif filtered with suction. Afterdrying one obtains 33 parts of the dyestuff of the formula CHZNHOO CHzClEXAMPLE 7 48 parts of the 1:1 chromium complex of the dyestulf 4 nitro 2aminophenol- 1 phenyl 3 methylpyrazolone 5 are dissolved together with50 parts of the dyestuif 2 aminophenol 4 chloroacetylaminomethylene 1hydroxynaphthalene, obtained according to Example 6, in 300 parts ofethylene glycol. The mixture is heated to 90 to 110 C., 150 ml. offormamide added and stirring continued for further 40 minutes. The

reaction mixture is then poured into 3000 parts of Water, acidified withdilute hydrochloric acid and filtered with suction. After drying oneobtains parts of the 2:1 chromium complex compound of the formula whichdyes synthetic superpolyamide fibres and wool brown shades.

EXAMPLE 8 A mixture of 53 parts of the azo dyestuff 5-nitro-2-aminophenol 4 chloroacetylaminomethylene l hydroxynaphthalene and 53parts of the dyestuff 4 nitro- 2 aminophenol 4chloroacetylaminomethylene lhydroxynaphthalene is dissolved in 500 partsof formamide and 200 parts of water, heated to to C. and treated with 60parts of ch-romiurn-(IID-chloride hydrate. The reaction mixture isstirred for 2 to 4 hours and then poured into 3000 parts of water. Theprecipitated dyestuff is filtered with suction, several times washedwith water and dried. One obtains 96 parts of the 2:1 chromium mixedcomplex dyestuff which dyes wool and synthetic superpolyamide fibresgrey to black shades.

EXAMPLE 9 28 parts of 4 chloroacetylaminomethylene-l-hydroxynaphthaleneare dissolved in 400 parts of water and 10 parts of 20% soda-lye. 40parts of sodium carbonate and a diazo suspension obtained bydiazotization of 13.7 parts of Z-aminobenzoic acid with nitric acid areadded Within 10 minutes. The reaction mixture is then stirred at pH 8 to9 for 4 hours, acidified with dilute hydrochloric acid, the dyestuffobtained filtered with suction and dried. One obtains 40 parts of thedyestulf of the formula COOH OH I CHBNHC 0 011201 The dyestutf dyessynthetic superpolyamide fibres yellowish red shades with good fastnessto washing.

EXAMPLE 10 24.6 parts of 4 ureidomethylene 1 hydroxynaphthalene aredissolved in 300 parts of water with 10 parts of 20% soda-lye, 40 partsof sodium carbonate and a diazo suspension obtained by diazotization of16 parts of 5 chloro 2 amino 1 methoxybenzene added within 15 minutesand the reaction mixture stirred for further 4 hours at pH 7 to 9. Themixture is then acidified with hydrochloric acid, the dyestuifprecipitated filtered with suction and dried. One obtains 35 parts ofthe CHzNHC ONH2 OOH;

C1 QM which dyes synthetic superpolyamide fibres red shades with goodfastness to washing.

I claim:

1. An azo dyestuff of the formula OH Y I i-N=N@ wherein A isunsubstituted or substituted benzene or naphthalene carrying the azogroup and Y in o-position to each other said substituents being selectedfrom the group consisting of chloro, nitro, sulphonic acid,sulphonamide, ethyl sulphone, methyl sulphone, hydroxyethyl,dimethylsulphonamide, methoxy methyl, hydroxy and methylene sulphoneether, Y stands for OH, COOH or lower alkoxy, R stands for hydrogen orlower alkyl, R stands for lower alkyl, lower alkenyl, lower alkoxy,phenyl, bromomethylphenyl, chloromethyl-phenyl, amino, mono loweralkylamino, di lower alkylamino or phenylamino or the metal complexcompounds of said azo dyestuft'.

2. The chromium complex or cobalt complex compound of the dyestuif ofclaim 1 having substantially one atom of chromium or cobalt bound incomplex union with two molecules of an azo dyestuif as least one ofWhich being a dyestuff of claim 1.

3. A metal complex dyestuff of claim 1 having one atom of cobalt orchromium bound in complex union with substantially two molecules of adyestufi of the CHzNHC O CHzCl wherein R stands for hydrogen, nitro,chloro or SO NH and R stands for hydrogen or nitro.

4. The 1:2 cobalt complex compound of a dyestuff of claim 1 having theformula CH2NHCOCH2C1 5. The 1:2 cobalt complex compound of a dyestuif ofclaim 1 having the formula CHzNHOO CHzCl 6. The 1:2 cobalt complexcompound of a dyestuff of claim 1 having the formula 7. The 1:2 cobaltcomplex compound of a dyestuff of claim 1 having the formula OzNHzCHzNHCOCHzCl 8. The 1:2 cobalt complex compound of a dyestufi of claim 1having the formula N0 (EHZNHCOCHZCI 9. The 1:2 chromium complex compoundof a dyestuif of claim 1 having the formula OH OH J1 (ilHaNHOOCHzCl 10.The 1:2 chromium complex compound of a dyestuif of claim 1 having theformula (EHzNHCOCHaCl References Cited UNITED STATES PATENTS 2,173,0549/1939 Hitch 260202 XR 3,114,746 12/1963 Benz et a1 260- XR 3,122,5332/1964 Senn 260150 XR 3,336,284 8/1967 Jager et al. 260154 FLOYD D.HIGEL, Primary Examiner U.S.Cl.X.R.

